Process and apparatus for manufacturing motor fuels



March 24, 1936. M P. YOUKER PROCESS AND APPARATUS FOR MANUFACTURINGMOTOR FUELS Filed Feb. 12, 1952 2 Sheets-Sheet l N .Sm

March 24, 1936. M P. YOUKER 2,035,209

PROCESS AND APPARATUS FOR MANUFACTURING MOTOR FUELS 2 Sheets-Shea?l 2Filed Feb. 12, 1932 BY I W ff Patented Mar. 24, 1936 j UNITED STATESPATENT oEl-iEf PROCESS AND APPARATUS Fort MANU- FAc'rUmNG Moron FUELSMalcolm P. Youker, Bartlesville, Okla., assigner I to Phillips PetroleumCompany, Bartlesville, Okla., acorporation of DelawareA ApplicationFebruary 12, 1932, scria1Nc.59z,s14

9 claims. (ol. 19e-5s) This invention relates to improvements inprocesses for converting hydrocarbon liquids or gases.

An object of the invention is to providea process by which gasolinehaving'a high antiknock rating and other desirable qualities may bemanufactured directly from crude oil.

Another object is to minimize the losses due 1 the novel featureshereinafter describeddn detail, illustrated in the accompanying drawingsand inore particularly pointed out in the ap pended claims.

The form of apparatus by vwhich my `new process is carried out isillustrated on the accompanying' drawings..

Figure 1 illustratesin elevation the complete 24. A part of the gaswhich will accumulate in apparatus.

Figure 2 is an elevationof the furnace 5 shown in Figure 1, the sidewall of the furnacebeing shown removed and the arrangement of theheating tubes and baille walls in the furnace thereby being revealedf 'lFigure 3 is a plan view. of the furnace 5, the top of which is shownremoved thus revealing the arrangement of the baille walls and heatingtubes in the interior of the furnace.

Crude oil will be delivered through the pipe I into the salt settler 2which is a horizontal cylindrical tank. A liquid level normally abovethe center of the salt settler 2 will-be maintained. Liquid will bedelivered from the tank 2 through the pipe 3 by means of the pump lthrough a furnace 5 and `into the'pipe I. The liquid thus.

delivered through pipe 3 will be heated in pass? ing through the furnace5 and being delivered into the pipe -I will mix with andheat the crudeoil liowing Ithrough the pipe I into the salt settler 2. As a result ofheating thecrude oil entering the salt settler 2, vapors will begenerated therein, and'these vapors will flow through lated in theaccumulator 9. lGasoline. may be Withdrawn from the accumulator 9through the valved pipe I0. Gases will be vented from the accumulator 9through vent pipe Il. Liquid will be withdrawn from the salt 'settler 2througha pipe I2 by a pump I3 and will b'e deliveredfby pump I3throughpipe I4 and thence through a heating tube I5 which passes throughfurnace 5 and delivers into thelower portion `of fractionating tower I6.A valve' I 'I which is mounted in heating tube I5 between furnace 5' andfrac` tionating tower I6 will be utilized to maintain pressure inheating tube I5. Liquid which is passed through the heating tube I5 beheated therein and will, upon entry into the and thelvapors thusgeneratedzwill flow upwar through the fractionating tower I6 and bubbletrays I8, and thence through pipe I9 and condenser 20.' and pipe 2| intothe gas-liquid sep arator 22. f

l5 fractionating tower I6, to a large extent vaporiz Ga-s which willaccumulate 1n the' separator 2z.

in gaseous condition will be vented therefrom through the pipe 23 inwhich is mounted a valve part of the liquefied. gas which willaccumulatev in the separator 22 will be delivered thence by pump 21throughpipe 28 in which is mounted valve 29 into the top offractionating towel` I6. l

'As a result of delivering said liquid through pipe 2B into the top offractionating tower I6, liquid reflux will ow downwardV throughfractionating tower I6over bubble trays I8 and will contact and condensea portion of the vapors which will rise through fractionating tower I6,and as a result of' said condensation, liquid, consisting of gasolineand'he'avier uid, wil1 accumulate in the fractionating tower I6. Liquidwhich will collect in the bottom of fractionating tower I6 will flowthence through pipe -28' -in A which is mounted a valve 29' into afractionating* tower 30 atA a`point below the bubble trays 3l ,which aremounted in fractionating tower 36.

Pressure will be maintained in fractionating tower I6 in excess of thepressure which will be 1 maintained in the fractionating tower 30, and,as

" a result, liquid flowing from fractionating tower I6 throughpipe 28into fractionating tower 30,

will partially vaporize upon entry into fraction- A suinoient quantityof the liquid which 'clay treater 33, pipe-34, and condenser' 35.

densate will flow from condenser 35 through Pipe '36 intoaccumulator 31.

gather inthe accumulator 31 will be pumped therefrom through pipe 38 bymeans of pump v39 into the top of fractionating tower 30 to maintain atemperature at the: top of fractinating t. tower 30 Asuch that onlygasoline vapors will pass therefrom to the condenser 35. Thus gasolineonly will be delivered intotheaccumulator 31. Gasoline will be withdrawnfrom accumulator he withdrawn therefrom through' a pipe l! in which ismounted avalve 53. These polymerized hydrocarbons may-either bewithdrawn to storage or theymay be delivered by means vof a pump lwhichis mounted in a pipe 55 into fractionating column 30. i

The pressure maintained in the salt settler- 2 7 will `be onlythat whichis set up therein by resistance to flow of vapors through the pipe 31through the -pipe I0 in which is mounted valve Gas will be' vented fromaccumulator 31 through vent pipe 42. As a result of introducing coldgasoline Ainto tl1e` top of fractionating tower 30, reflux liquid-williiow downward over bubble l intermediate points along the 'heating tubeI5.l

' plates 3l and will condense that part of thevapors arising j throughfractionating tower 30 which is heavier than gasoline. Distillate whichis heavier than gasoline may be withdrawn from one of the bubble trays3l which is intermediate betweenthe point/of entry of pipe 28T infractionating tower 30 andthe top of fractionating tower 30 through apipe I3 in which is mounted a valve 44. Distillate will be delivered -bya pump from one of the bubble plates 3I through afpipe V46 which willpass through furnace 5 and lead into-the pipe 28'. The liquid whiclrwillbe passed through pipe I6 will be heated in passage through furnace 5and will, upon entry into the pipe 23", heat tle liquids which will Ilow fro1` the fractionating tower Il through the pipe 28'. y Fuel oilwill bewithdrawn from the bottomof Yfraetionating tower 30 'through pipe41 in which is mounted valve 48- A pipe 49 .in which is mounted a valve50 will serve to conduct 'liquid from an intermediate one of the bubbletrays I8 in fractionating tower I6 into fractionating tower 3l at apoint above the entry point of pipe 2 8 into fractionating tower 30. 5

A'conv'entional caustic washer 5I"is mounted in the .pipe'25 and servesto remove hydrogen sulde and'other impurities from the liquefied` geswhich hows through the pipe z5.

A pump 56 is mounted in a pipe 51in which is mounted a valve 58 andwhich leads into heating tube I5 by means of which straightrun gasoline,hydrocarbon gas, eitherin liquid or gaseous form, 'fuel oil, lhydrogen,or any other hydrocarbon material or treating agent may be introducedinto and passed through the heating tube I5. I may elect to delivergasoline collected Vin the accumulator 3 into and through the heatingtube I5 by will be less than3000 pounds per square inch bythe amount offriction heat between the point of which such pressure is taken Aandsaid pumps. A pressure of between 200 pounds per square inch and 1000pounds per square inch,

The pressure maintained in the fractionating column 30, the clay treater33, the condenser 35 and inter-connecting lines will beonly in excess'-ofatmospheric pressure, to the extent that pressure is set up. byreason of the resistance to flow of vapors and condensate throughsystem, as the accumulator 31 will be operated at approximatelyatmospheric pressure..

'I'he length ofthat part of the pipe 3 which will be `exposedgto heat inthe furnace 5 will be so proportioned that the'liquid whichwill enterthe salt' settler 2 will be heated to about 250 F. Therefore, nothingheavier than gasoline-will be vaporized in the salt settler 2.

By regulation of the quantity of fuel red in the furnace .5,theftemperature to which the liquid passed through heating tube I5 willbe heatedwill vary between 800" F. and 900 F., and this temperature willpreferably be 4between 845 F. and 865 F.

s'uch that the vapor pressure of the liquid leavmeans of thel pump'56and the-valved pipe 59.

Water or water containing treating agents, `either in suspension or insolution, -or treating agents alone, may be introduced through valvedsalt settler 2 will flow slowly through `this salt 'io iiow. throughthis body or oiayiand intimately pipe 6l into the heated hydrocarbonwhich will ilow'from the fln'nace 'throughfheating tube I5 intoireotionating tower ls.

' Crude loil being preheated and delivered into settler and any saltcontained inthe crude, .as well'as other debris, be settled from the'`crudetherein and will be periodically rebe in accord with the currentspecifications for .motor fuel, which at this time vary between 8 poundsper square inch and 13 pounds per The temperatures maintained atthetop'of' thefractionating tower -I6 by means of regulating thedelivery lof rer-N flux vliquidv 'into the top `of this tower-willbesquare inch when taken-by the Reid method at F.' That part'of they pipe46 which will be exposedfto heat in .the furnace 5.will be soproportioned that the bottom of the. fraction- `ating tower 30v beheated to the extent necessary to remove from the liquids which will,

collecty in -the bottom of fractionating tower 30 practically allgasoline fractions.

The heating tube I5 is divided into a heating portion and a conversionportion after the manner which has already been disclosed' in ap.

plications for pa.tent filed by the-present ap-l Ahody of fuuers earth'wiuhe so disped' ln the clay treater- 33 that vapors may readilyl tweenvapors and fullers'. therein, will clay treater 33 as 'a result of the'contact be plicant'under cations:

U'. S. Serial No.'559,083, filed- August 24, 1931;

. U. S. 'Serial N0. 545,309', :Bled-June 18, 1931;

: U.. S. 1al 110,579,044, Bled-December 4,

the following listed patent appliheating tube I5 of the materials passedtherethrough, -it isdesirableto first rapidly heat these materials toconversion temperatures in the first part of theheating tube I5 and thenpass the thus heated material through a latter portion of the heatingtube I5 which is .so arranged in thefurnace as to be,only mildly 5.-.The quantity of liquid which will `be pumped' heated.

Referring to Figures 2 and 3 of .the drawings,

it will be noted that the interior of the furnace 5 is so partitioned onby a bridgewall 6I and a. baille wall 62 that acombustion chamber isformed between bridge wall6 Il and the end wall 6 9 of -theffurnace andthat gases ofcombustion developed'in this combustion chamber arerestricted to flow upward over the top of bridge wall 6I thence downwardthrough apas'sageway between bridge -wall 6I and baille wall 6 2 thenceunder baffle wall 62 and thence upwardthrough a psage-way between bridgewall 6.2 and the adjacent end wall 'I0 of the .furnace and thencethrough a breeching'l 63 in .which is mounted a damper 64 and thenceupward througha smoke stack' 65. 'A breeching 66 in which is mountedafan '6l and adamper 68 is interconnected between the bottom of saidlast-mentioned passageway between said baffle wall and said adjacent endwall and the bottom of said smokey stack 65.

' The fan 61jmay be operated toforce gases of combustion from the smokestack into the fur- 'nace, thus recireulatinggases of combustion throughsaid last-mentioned passage-way, .or

said fan may be allowed to remain stationary in i which case gases ofcombustion will flow from j the furnace into the smolg stack throughthebreeching 66J and in either case the damper 68 may be' used toregulatethe ow of gases. of comb'ustionthrough lthe breeching 66.Temperature 'recording devices not shown on the drawings areof. courseinstalled at the-junction 'of the heating portion and the conversionportion and at the outlet of the heating tube I5 to indiing tube I5which is utilized f or the rapid heat-v ing of the materials passedtherethrough `to .conversion temperature is so disposed over thecombustion chamber and in the. passage-way between bridge wall '6I andbafe wall 62 that gases of `combustion developed in the-combustionchamber immediately and before contacting any other heat absorbingsurface are contacted Ving tube I5 -in which conversionof the materialspassed therethrough takes place is disposed in ingtube I5.. Thatportionzof the pipe 3 which passes through furnace 5 is'disposed in thepassage-way between the baille wall 62 and the adjacent end wall 10 ofthe furnace in a posi- That- It will be seen that .the ow of gases ofcombastion through the furnace s is such thai, these f gases firstcontact the heating portion offthe heatingvtubey I5; second,contact-'that portion of the pipe 46 which passes through the furnace 5;

. 3 tion above the conversion portion of the heating 'tube I5..

third, contact the. conversionportion ofl the heating tube I5: and,fourth, contact that-part vof the pipe which passes throughthe furnacethrough the pipe 46 will be so regulated and .the j length and size ofthat portion ofthe pipe 46.

which is disposed the furnace 5 wil1"`be so proportioned as to reducethe. temperature of.l the gases of combustion passing around the pipe 46to-any desired temperature before these gases contact the conversion.portion ofthe heating tube. I5. Increasing theow of oil through pipe 46'cool the gases of combustion passing over the conversion .portion of theheating tube I5 to anydesired temperature and i'n this .way heat. f

transfer .from the gases of combustionV to the conversion ortion of thevheating tube I5 may.v 425 be caused take place/at a low rate andthequantity'of 'heat so transferred may be regulated. y

I t lis lapparent that some other stream of liquid f mightbe passedrthrough the-pipe 46 to accomplish thispurpo'se and that my reasons forusing@ I the particular'-stream of liquid designated arev economic. f uThe mannerV `in-whicli the breeching 66, to-

. gether with the fanv 6l and the damper 68, may

-be advantageously used to abstract gases of combustion from the furnacebefore the same have passed over the conversion portion of the Aheatingtube I5 or to force recirculation. of gases t from the s mke stack backinto the furnace and over said conversion portion of said tube isalready disclosedl inthe above-mentioned patent application Serial No.579,044 previously' filed by the present applicant. Circulating gases ofcombustion-from the bottom of the vsnroke stack 'I 65 bymeans of the fan61 through the breeching 66finto-the furnace and thence upward throughthe'passage-way between bale'wal1f62 and end wall 'III and' thencethrough breeching A63 into smokestackSS in regulated quantities willv12e-f sult in` regulated cooling of the gases of combustion prior totheir passage over the .conversion portion of heating'tube I5, thuspermittingjegulated lmoderate heating of the materials passing whichwill ow over the conversion portion ofthe heating tube I5 and will thusresult in .the

regulated moderaten heating of the' materials passing through theconversion-.portion of the therewith. 'The conversion portion of theheathea g tube 's' y It should be noted that while nally contactpipe 3is an economic arrangement theprincipally advantageousl feature ofthefurnace and heating arrangement shown is that the y lgases of combustionafter being contacted with the heating portion of the heating tubo iscooled by being contacted withy the heating pipe -ing gases ofcombustion with thepreheating 46 before being contacted with theconversion I The maieriais passed through the heating 'tubo I should beheated in passing therethrough to a maximum temperature in the heatingportion of this tube and the temperature of these materials should notthereafter be increased in passing through the conversion portionof'thetube. In other words, a portion of the heating tube I5 adjacenttothe exit end of said tube should be heated in a manner such that onlyheat absorbed by the conversion-reaction is sup',- plied 'to thematerials flowing therethrough and such that the temperature of suchmaterials is not increased in passing thrbugh this latter portion ofsaidhe'ating. tube. The conversion portion of theheating tube I5shouldbe of substantial length. While some results may be obtained byusing a three irich inside diameter tube as short as 500 feet, itis'desirable 'to use a three inch inside diameter tube atleast 2,000

feet long, and preferably 3,000 or 4,000 feet long, for conversionpurposes, throughwhicli the material to be converted is' owed after suchmaterial has been brought to conversion temperature. While I havedescribed thedesirable conditions which should be'obtaned in theconversion portion of the heating tube I5, I.would) -say that in orderto obtain results suiiciently 2practical to permit commercial ioperationit isv absolutely necessary that not less than the lat'- .ter soounemfeet of tne'heating tube ls 'bematerials passing throughfthe latterportion `of nd that 'maintaining temperatures of f approxi-- theconversion of the fuel oil lwhen operated 5s and outlet of theconversion portionlofthe heat- I 1 for the jconverson of crude' oils themay alsobe advantageously utilized for the oonof steps cutanea herein;that 18,'by-1pass1ngtne .,"same through the heating tube Iiin the maur`70 supplied with heat Ain quantity such that the temperature vof thematerials passing therethrough berased n ot more than two degreesFahrenheit per d100 feet of :travel through said) latter portion ofheating tube I5 andas stated above heat should preferably be supplied tothe said heating tube in considerably less than this quantity. f i' Themaximum advantageous temperature to be` used will .be found to vary withthe type of material vundergoing conversion. I have constructed and havein operation two heating tubes y to thevheating tube I5` hereindescribed, one of which is used for the ,conversion of heavy fuel oiltogasoline and ga's oil andcne of whichf is used forconverting gas oilto gasoline. I

mately v850" F. and840 `respectively, at 'the inlet and the outlet ofthe conversion portion of the' heating tube obtains very goodresults inunder a pressure of about 350il pounds per-square inch, while for theadvantageous conversion of' gas oil temperatures of approximately 885 F.

and'875 F., respectively, maintained at the inlet ing tube appear to bethe best temperatures when operating under about 350 pounds per'square'inch pressure. It should be noted thatl vwhile the presentprocess is speciilcally outlined* for and appears to be particularlyadvantageous version of other oils such as fuel oil or gas oil.

It appears that the conversion of oils, which: already contain gasoline,to gasoline may -be acvcomplished particularly well bythe combinationner described1 under a'pressure upwards 'of 1,500

pounds per square inch particularly theA anti-- knock-rating ofthegasoline as a whole thus produced from crude oils is high. While I havedescribed in detail a method b y which my new process may be out; itlis- -broadly all of the advantages lliquids comprising passing said`hydrocarbon liquids'rst through a heating portion of a tube heated bycombustion gases at a hightempera- -through a conversion portion of,said tube `overrsaid heating to be understood that I do' not intend toliinit1 1 my claims to these details but lintend to`c1aimv l which areinherent 1.- An apparatus of the character described,

comprising a furnace havinga passageway therethrough, means for creatinghot gases' of combustionat one end portion of said passageway, meansfor;v discharging combustionggasesfrom the' other end portion of saidpassageway, an oil heating ltube ext nding through said passageway andincluding heating portion and a conversion portion, a irst fractionatingtower con` nected to the outlet end of said tube, a second Ifractionating tower, a pipe for leading liquid- `from the firstfractionating tower-to aninterof the passageway andfpassing to th'eother end portion of said passageway will pass rst. over theheatingportion ofthe oil heating tube, second over said portion of thereheating tube, and third over said conversion portion of heating 2. Afor ,the conversion of hydrocarbon ture wherein the hydrocarbon liquidsareraised to a cracking temperature and afterwards whereinthe'hydrocarbon liquidsare maintained at a cracking temperature bypassing combustion Y gases v'of lower temperature. than said first namedcombustion, gases in heat exchange with said' j* conversion portion ofthe tube, passing oil from atdiiferent point of,l supply through aheating coil and hot gasesof combustion first.

over the vheating portion vof said tube, secondr coil and third oversaid conversion portion of said tube.- l

3. 'A process for the conversion of hydrocarbon liquids, comprisingpassing said' liquidsl ilrst through a heating'portioii of a ,tubeheatedby combustiongases ata'high'temperature wherein thehydrocarbon'linuidsare raised toa cracking *temperature andafterwards-through aconversion portion of said tube wherein thehydrocarbon Aliquids are maintainedat a' cracking `tem perature bypassing combustion gases of lower temperature than'said first'namedcombustion 30 l gases in heat exchange with said conversion portionofthe `tube', reheating hydrocarbon liquid 1 .resulting fvromf the'processin a heatingjcoil,

preheating hydrocarbon'liquidina -preheating coil thenpassing some ofthe last mentioned liquidl vinto the inlet of the .heating tube,

and passing gases-of combustiomrst over said lieatingportionofsaidtuba-seoond'over 4.said y heating coil, third over(l said conversionportion '0f Said tube. coil.

4. A process for the conversion of hydrocarbon liquids comprisingheating such 'liquids to..less

`than crackingv and-then separating occurring gasoline from theremainder '75 y freer-rh er eid ammi@ of the liquids, then passing` saidremainder of the liquids rst through aheating portion of a tube heatedby combustion gases' at a high temperature wherein the hydrocarbonliquids are raised to a cracking temperature and afterwards through aconversion portion of said tube wherein the hydrocarbon liquids aremaintained at a cracking temperature by passing `combustion gases oflower temperature than said first named.combustion gases in heatexchange with said conversion portion of the tube, passing oil from adifferent point of supply through a heating coil, and passing hot gasesof combustion -rst over the heating portion of said tube, secliquids areraised to a cracking temperature, and

afterwards through a conversion portion of said tube wherein thehydrocarbon liquids are maintained at a cracking temperature by .passingcombustion gases of lower temperature than said first named combustiongases in heat exchange with said conversion portion of the tube, passingoil from a dierent point of supply through a heating coil and passinghot'gases of combustion rst over the heating portion o f said tube,second over the heating coil, and third over the conversion portion ofthe saidtube, a part of the said gasoline being mixed with saidremainder of the liquids before the mixture is introduced into theheating portion of the tube.

6. A process for the conversion of hydrocarbon liquids, comprisingpassing said liquids rst through a heating portion of a tube heated bycombustion gases at a high temperature wherein the hydrocarbon liquidsare raised to a cracking temperature and afterwards` through aconversgin portion of said Vtube whereinthe hydrocarbon liquids aremaintained at a cracking temperature by passing combustion gases oflower temperature than said first .named combustion 'gases in heatexchange with said conversion porreheating coil, and third, over saidconversion portion of said tube. l

. 7. A process for the conversion of hydrocarbon liquids, comprisingfirst passing said liquids through a preheating pipe and heating thesame therein to a'. temperature insufficient for cracking but suiiicientfor the evaporation of naturally occurring gasoline from the remainingliquid, then separating said gasoline from the remaining liquid, thenpassing said remaining liquid through a heating portion of a tube heatedby combustion gases at a high temperature wherein the said remainingliquid is raisedV toa cracking temperature and afterwards through aconversion portion of said tube wherein the said remaining liquid ismaintained at a cracking temperature by passing combustion gases oflower temperature than said rst named combustion gases in heat exchangewith said conversion portion of the tube, passing oil from a diierentpoint of supply through a heating coil and passing hot gases koi"combustion first over the heating portion of said tube, second over saidheating coil,.third over said conversion portion of said tube and fourthover said preheatingY pipe.

8. A process for the conversion of hydrocarbon liquids comprisingpassing said hydrocarbon liquids through a primary portionof a tubeheated by combustion gases wherein the hydrocarbonliquids are raised toa high temperature and afterwardsthroughv a secondary portion of saidtube wherein the hydrocarbon liquids are maintained at saidtemperatureby passing combustion gases of lower temperature than saidiirst named combustion gases in heat exchange with said secondaryportion of the'l tube, passing liquid oil from a different point ofsupply through a heating coil and passing hot gases of combustion rstover the primary portion of. said tube, second over said heating coiland third over said secondary portion of said tube.

9. A process for the conversion of hydrocarbon fluids comprising passinga hydrocarbon fluid through a primary portion of a tube heated bycombustion gases wherein said fluid is raised to a high temperature andafterwards through a secondary portion of said tube wherein thehydrocarbon uid is maintained at said temperature by passing combustiongases of lower temperature than said first named combustion gases inheat exchange with said secondary portion of the tube, passing anotherhydrocarbon, uid fim a different point of supply through a heating coil,and passing hot gases of combustion iirst over the primary portion ofsaid tube, second over the heating coil and third over said secondaryportion of said tube.

MALCOLM P. YOUKER.

